WO2002081414A2 - Hydrogenation supercritique - Google Patents

Hydrogenation supercritique Download PDF

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Publication number
WO2002081414A2
WO2002081414A2 PCT/GB2002/001387 GB0201387W WO02081414A2 WO 2002081414 A2 WO2002081414 A2 WO 2002081414A2 GB 0201387 W GB0201387 W GB 0201387W WO 02081414 A2 WO02081414 A2 WO 02081414A2
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
catalyst
substrate
hydrogen
product
Prior art date
Application number
PCT/GB2002/001387
Other languages
English (en)
Other versions
WO2002081414A3 (fr
Inventor
Stephen Keith Ross
Nicola Jane Meehan
Martyn Poliakoff
Daniel N. Carter
Original Assignee
Thomas Swan & Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thomas Swan & Co Ltd filed Critical Thomas Swan & Co Ltd
Priority to KR10-2003-7013052A priority Critical patent/KR20040002898A/ko
Priority to EP02718304A priority patent/EP1373166A2/fr
Priority to JP2002579402A priority patent/JP2004534012A/ja
Priority to CA002442926A priority patent/CA2442926A1/fr
Publication of WO2002081414A2 publication Critical patent/WO2002081414A2/fr
Publication of WO2002081414A3 publication Critical patent/WO2002081414A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P25/00—Drugs for disorders of the nervous system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method of carrying out a chemical reaction, which involves hydrogenation of a substrate using a heterogeneous catalyst under conditions of continuous flow in a continuous flow reactor.
  • the present invention also concerns reactions such as hydroformylation and reductive amination and these reactions fall within our definition of hydrogenation.
  • the reaction is performed in the presence of a supercritical fluid.
  • the single phase may be obtained by working at high pressure or at a low concentration of substrate in the fluid. In either case this makes the industrial processes less economic than if this reaction could simply be achieved with a mixed phase system.
  • SCF supercritical fluid
  • amines mainly primary and secondary organic amines, but not exclusively such amines
  • react with supercritical carbon dioxide to form solid carbamates, which may precipitate within the flow system. This may cause fouling of the catalyst and/or the equipment.
  • a co- solvent for example methanol
  • methanol methanol
  • the use of a co-solvent is in general disadvantageous because many co-solvents have the problems of environmental toxicity, high flammability and the requirement for further separation. This applies particularly if use is made of a flammable fluid such as a hydrocarbon or an environmentally toxic fluid such as a halocarbon.
  • a process for the hydrogenation of a hydrogenatable substrate which is carried out in a continuous flow reactor as a mixed phase system over a heterogeneous catalyst, which system comprises one or more substrates, hydrogen or a hydrogen transfer agent and one or more products and optionally a co-solvent and includes a supercritical fluid, in which system at least one substance selected from substrate (s) , product (s) and co-solvent forms a separate phase from said supercritical fluid.
  • the process of the present invention is thus capable of effecting selective hydrogenation of one or more functional groups and/or positions of unsaturation in the compound in preference to other functional groups and/or positions of unsaturation which may also be present in the compound.
  • the process of the invention enables hydrogenation of one functional group to be effected in a molecule in preference to another functional group of the same or different type in the same molecule.
  • the appropriate conditions for producing a chosen product from a particular substrate are determined in a trial run for given catalyst by varying one or more of the temperature, pressure, flow rate and H 2 concentration. The process is then carried out under those conditions. Limited work has been carried out in the literature on trying to use biphasic media such as with hydrogenations in aqueous/supercritical media (Chem. Commun, 2000, 941-2) .
  • the supercritical fluid is used not to provide a single phase and eliminate the mass transport boundary but acts by reducing the viscosity of the reaction system sufficiently to effect good mixing of the reagents. In this manner an efficient reaction is achieved.
  • nitrogen as a supercritical medium is particularly relevant industrially as amines and nitro compounds (as reactants or products) can be mixed with supercritical nitrogen and hydrogenated without reacting with the supercritical fluid and without reverting to a fluid that is flammable or highly toxic to the environment if exposed thereto .
  • the use of mixed phase hydrogenation of the present invention also simplifies the design of chemical manufacturing plant in that no decompression stages are required for collection of the product, so that the plant may be operated at a constant pressure. This reduces the capital and operating costs, making the process more economically viable.
  • This system therefore gives all the benefits outlined in W097/38955 but with simplified equipment and does not require the high pressures required to give a single phase. It also means that a higher loading of substrate to fluid can be used than was previously thought possible. Thus, in the present invention a substrate loading of more than 4% can be achieved and preferably at least 8%. In one embodiment, solid substrates which cannot be added as melts can be added dissolved in a co-solvent. This may give rise to even more complex behaviour yet still gives good conversion and selectivity.
  • the present invention effects hydrogenation of a substrate under conditions in which a fluid which is supercritical is present.
  • supercritical is used herein to denote a fluid which is above its critical temperature and pressure or at conditions below supercritical at which the density of the fluid is sufficient to ensure that one but not all of the reactants and/or products and/or added co-solvent, if any, is/are substantially in a single phase with said fluid.
  • supercritical as used herein also refers to reaction conditions in which the viscosity of the reaction system is reduced sufficiently to enable good mixing of two or more distinct phases to be achieved. Hence it is possible to obtain the required hydrogenation product in good yield.
  • the catalyst bed and/or an additional pre-mixer can achieve the mixing.
  • hydrogenation as used herein is meant any reaction- in which hydrogen or an isotope of hydrogen (e . g. deuterium) or a hydrogen transfer agent (e . g. formic acid) is an active agent.
  • Such reactions include hydrogenolysis, saturation reactions, reductive alkylation/amination and also hydroformylation, as all these require addition of hydrogen to a substrate.
  • the substrate or group to be hydrogenated is typically, but not exclusively, is selected from: alkene, alkyne, lactone, anhydride, cyclic anhydride, amide, lactam, Schiffs base, aldehyde, ketone, alcohol, nitro, hydroxylamine, nitrile, oxime, imine, azine, hydrazone, azide, cyanate, isocyanate, thiocyanate, isothiocyanate, diazonium, azo, nitroso, phenol, ester, ether, furan, epoxide, hydroperoxide, ozonide, peroxide, arene, saturated or unsaturated heterocyclic, halide, acid halide, acetal and ketal .
  • the substrate or group is selected from: alkene, Schiffs base, nitro, hydroxylamine, nitrile and nitroso .
  • reaction mixture (c) exposing the reaction mixture to a heterogeneous catalyst to facilitate the selective reaction; and (d) removing the reaction mixture after reaction from the region of the catalyst and isolating the desired product by depressurisation of the reaction mixture.
  • the process is applicable to substrates for which there is only one possible product. In such cases, the process ensures a high yield of the desired product .
  • the process of this invention preferably comprises the steps of:
  • the multi-phase continuous flow system of the present invention offers a number of advantages compared with a homogenous continuous flow system.
  • the present invention allows the formation of a desired end product in a selective manner by controlling one or more of: the temperature, the pressure of the reaction, by varying the catalyst used for a given set of reagents, and the flow rate through the apparatus.
  • the factors controlling the selectivity of hydrogenation will depend on the particular reaction and in some instances the temperature or the pressure will be the controlling factor, whereas in other cases the catalyst or flow rate may be more important in determining the outcome of the reaction.
  • two or more reaction zones can be placed in series to effect different hydrogenation reactions as exemplified in W097/38955 (except that in the present case the reactions are all carried out in a mixed phase system) .
  • the details of this feature are thus specifically incorporated herein by reference.
  • the catalysts used can be any heterogeneous catalysts, the choice of metal and support depending on the identity of the functional group (s) to be hydrogenated.
  • the catalyst used in the process of this invention preferably comprises a carrier and a metal selected from platinum, nickel, palladium or copper or a combination thereof, and optionally a promoter.
  • Particularly favoured media to have in the reaction system as component in a supercritical condition include carbon dioxide, sulphur dioxide, nitrogen, alkanes such as ethane, propane and butane, alkenes, ammonia, and halocarbons such as trichlorofluoromethane, dichlorofluoromethane, dichlorodifluoromethane, chlorotrifluoromethane, bromotrifluoromethane, trifluoromethane, and hexafluoroethane.
  • the choice of supercritical fluid is only limited by the engineering constraints but particularly favoured fluids are carbon dioxide and nitrogen, and nitrogen is of particular interest.
  • reaction medium may be a mixture of two or more fluids having critical points which do not require commercially unacceptable conditions of temperature and pressure in order to achieve the necessary conditions for reaction according to the present invention.
  • mixtures of carbon dioxide with an alkane such as ethane or propane, or a mixture of carbon dioxide and sulphur dioxide may be employed close to or above their theoretical critical points.
  • hydroformylation also known as the "oxo process”
  • this is used for large-scale production of aliphatic aldehydes and alcohols from olefins (alkenes) using cobalt- or rhodium-based homogeneous catalysts.
  • the hydroformylation reaction involves reaction of an alkene or alkyne with a mixture of carbon monoxide and hydrogen over a catalyst at high pressure to produce a carbonyl compound. Mixtures of hydrogen and carbon monoxide are frequently referred to as synthesis gas or syn gas.
  • the catalyst comprises a support and a metal or metal complex in which the metal is selected from: platium, nickel, palladium, cobalt, rhodium, iridium, iron, ruthenium, and osmium, and the catalyst optionally includes a promoter.
  • Rhodium is a particularly preferred metal.
  • the multiphase reactions of this invention can be used to achieve selectivity in respect of reaction product when -lithe substrate is capable of yielding more than one reaction product.
  • Prior experiment may be carried out, varying one or more of temperature, pressure, flow rates, H 2 concentration for a given catalyst to produce products differing as to product identity, as well as product, yield, and, with a set of conditions then defined for a particular product, working in accordance with such conditions.
  • the lower limits of the conditions suitable for supporting the hydrogenation reaction are conditions of temperature and pressure at or just below the critical point of the fluid.
  • the upper limit is governed by limitations of the apparatus .
  • Substrate 1 dissolved in an appropriate solvent if it is a solid, is pumped into mixer 2 which may be a mechanical or static mixer where it is mixed with fluid 3 which is to be supercritical and which has been delivered from reservoir 4 via pump 5.
  • Hydrogen 6 is delivered from reservoir 7 via compressor 8 and a dosage unit 9 to mixer 2.
  • the hydrogen pressure is typically 20-50 bar higher than the pressure at which fluid 3 is supplied.
  • the hydrogen is added via a switching valve or similar control to give the required hydrogen to substrate ratio, the actual ratio being dependent on the particular hydrogenation reaction being carried out.
  • the temperature and /or pressure of the reaction mixture is adjusted to a temperature and pressure just below, at or above the critical point of the fluid 3 as required. Heating means 10 is provided for this purpose.
  • This control of conditions can also be achieved by heating/cooling the reactor or a combination of both.
  • the mixture is then passed into reactor 11 which contains a catalyst (not shown) fixed on a suitable support. After an appropriate residence time the mixture is passed into pressure reduction unit 13 and the product removed via take-off tap 14. The flow rate of the mixture through the reactor is controlled by a valve (not shown) in pressure reducer 13. Fluid 3, together with any unconsumed hydrogen is vented through relief pipe 15 to atmosphere.
  • This reaction was conducted in the presence of supercritical nitrogen in a mixed phase system (0.5 mL/min benzaldehydes in excess ethanol solution in 0.65 L/min flow with 3 equivalents of hydrogen at a pressure of 100 bar) . This is equivalent to 41% benzaldehyde in the supercritical fluid.
  • the reaction was carried out in apparatus shown schematically in Figure 1 using the procedure described previously in relation to Figure 1. The reaction gave 100% conversion to benzylamine at 100°C.
  • the catalyst was a Deloxan 5% Pd catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Biomedical Technology (AREA)
  • Neurology (AREA)
  • Neurosurgery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé d'hydrogénation de substrat en présence de fluide supercritique, visant à assurer la présence de plusieurs phases dans le milieu de réaction. La réaction est soumise à des conditions continues. On améliore ainsi le rendement relatif à l'élaboration des produits hydrogénés. En outre, ce procédé permet d'engager sélectivement l'élaboration d'un produit spécifique lorsque le processus peut déboucher sur la réalisation de plusieurs produits.
PCT/GB2002/001387 2001-04-06 2002-04-04 Hydrogenation supercritique WO2002081414A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR10-2003-7013052A KR20040002898A (ko) 2001-04-06 2002-04-04 초임계 수소화반응
EP02718304A EP1373166A2 (fr) 2001-04-06 2002-04-04 Hydrogenation supercritique
JP2002579402A JP2004534012A (ja) 2001-04-06 2002-04-04 超臨界水素化
CA002442926A CA2442926A1 (fr) 2001-04-06 2002-04-04 Hydrogenation supercritique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0108775.8 2001-04-06
GB0108775A GB2374071A (en) 2001-04-06 2001-04-06 Hydrogenation reactions using supercritical fluids

Publications (2)

Publication Number Publication Date
WO2002081414A2 true WO2002081414A2 (fr) 2002-10-17
WO2002081414A3 WO2002081414A3 (fr) 2002-12-12

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EP (1) EP1373166A2 (fr)
JP (1) JP2004534012A (fr)
KR (1) KR20040002898A (fr)
AR (1) AR033458A1 (fr)
CA (1) CA2442926A1 (fr)
GB (1) GB2374071A (fr)
WO (1) WO2002081414A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005056182A1 (fr) * 2003-12-08 2005-06-23 Boehringer Ingelheim International, Gmbh Elimination de sous-produit de ruthenium par traitement fluidique supercritique
WO2006063456A1 (fr) * 2004-12-17 2006-06-22 University Of New Brunswick Synthèse, recharge et traitement de matériaux d’entreposage d’hydrogène utilisant des fluides supercritiques
JP2007111693A (ja) * 2003-11-19 2007-05-10 Scf Technologies As 高密度流体プロセスの温度、圧力、密度を制御する方法とプロセス
EP2546244A1 (fr) 2011-07-13 2013-01-16 Koste Biochemicals Procédé supercritique de fabrication d'ambradiol, de sclaréolide et (-)-ambrafuran à partir de sclaréol
CN112390727A (zh) * 2019-08-16 2021-02-23 沈阳中化农药化工研发有限公司 一种羧酸肟酯类化合物及用途
CN113214863A (zh) * 2020-07-10 2021-08-06 中国石油大学(北京) 一种馏分油超/亚临界流体强化加氢方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7408009B2 (en) 2002-11-05 2008-08-05 North Carolina State University Hydrogenation of polymers in the presence of supercritical carbon dioxide
JP4734505B2 (ja) * 2005-01-26 2011-07-27 独立行政法人科学技術振興機構 マイクロリアクター及びそれを用いた接触反応方法
KR100780910B1 (ko) * 2007-01-24 2007-11-30 한국에너지기술연구원 니켈/활성탄 촉매 제조방법 및 니켈/활성탄 촉매를 이용한유기물질의 초임계수 기화에 의한 수소제조시스템 및 그운전방법
JP5376357B2 (ja) * 2008-08-23 2013-12-25 独立行政法人産業技術総合研究所 超臨界二酸化炭素流体によるｈｍｆの水素化、開環による直鎖アルカンの製造方法
DE102010009346A1 (de) * 2010-02-20 2011-08-25 Fachhochschule Münster, 48565 Synthese von 2-Carboxy-3,5,5-trimethylcyclohexan-1-on
JP5565799B2 (ja) * 2010-04-22 2014-08-06 独立行政法人産業技術総合研究所 超臨界二酸化炭素中における有機ニトリル化合物の水素化物の製造方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
US6156933A (en) * 1996-04-17 2000-12-05 Degussa-Huls Ag Supercritical hydrogenation

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
WO2002002218A1 (fr) * 2000-07-01 2002-01-10 The University Court Of The University Of St. Andrews Catalyse dans un systeme biphasique fluide ionique-fluide supercritique

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Publication number Priority date Publication date Assignee Title
US6156933A (en) * 1996-04-17 2000-12-05 Degussa-Huls Ag Supercritical hydrogenation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BERTUCCO A ET AL: "CATALYTIC HYDROGENATION IN SUPERCRITICAL CO2: KINETIC MEASUREMENTS IN A GRADIENTLESS INTERNAL-RECYCLE REACTOR" INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, AMERICAN CHEMICAL SOCIETY. WASHINGTON, US, vol. 36, 1997, pages 2626-2633, XP000827943 ISSN: 0888-5885 *
BONILLA, R.J. ET AL.: "Colloid-catalysed arene hydrogenation in aqueous/supercritical fluid biphasic media" CHEM. COMMUN., 2000, pages 941-2, XP002215215 cited in the application *
DEVETTA, L. ET AL.: "Linetic experiments and modeling of a three-phase catalytic hydrogenation reaction in supercritical CO2" CATALYSIS TODAY, vol. 48, 1999, pages 337-45, XP002215214 cited in the application *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007111693A (ja) * 2003-11-19 2007-05-10 Scf Technologies As 高密度流体プロセスの温度、圧力、密度を制御する方法とプロセス
JP2007511357A (ja) * 2003-11-19 2007-05-10 エスセーエフ テクノロジーズ アクティーゼルスカブ 高密度流体プロセスの温度、圧力、密度を制御する方法とプロセス
WO2005056182A1 (fr) * 2003-12-08 2005-06-23 Boehringer Ingelheim International, Gmbh Elimination de sous-produit de ruthenium par traitement fluidique supercritique
US7268211B2 (en) 2003-12-08 2007-09-11 Boehringer Ingelheim International Gmbh Removal of ruthenium by-product by supercritical fluid processing
WO2006063456A1 (fr) * 2004-12-17 2006-06-22 University Of New Brunswick Synthèse, recharge et traitement de matériaux d’entreposage d’hydrogène utilisant des fluides supercritiques
EP1843973A1 (fr) * 2004-12-17 2007-10-17 University Of New Brunswick Synthèse, recharge et traitement de matériaux d'entreposage d'hydrogène utilisant des fluides supercritiques
EP1843973A4 (fr) * 2004-12-17 2013-08-07 Univ New Brunswick Synthèse, recharge et traitement de matériaux d'entreposage d'hydrogène utilisant des fluides supercritiques
EP2546244A1 (fr) 2011-07-13 2013-01-16 Koste Biochemicals Procédé supercritique de fabrication d'ambradiol, de sclaréolide et (-)-ambrafuran à partir de sclaréol
CN112390727A (zh) * 2019-08-16 2021-02-23 沈阳中化农药化工研发有限公司 一种羧酸肟酯类化合物及用途
CN112390727B (zh) * 2019-08-16 2021-12-07 沈阳中化农药化工研发有限公司 一种羧酸肟酯类化合物及用途
CN113214863A (zh) * 2020-07-10 2021-08-06 中国石油大学(北京) 一种馏分油超/亚临界流体强化加氢方法

Also Published As

Publication number Publication date
CA2442926A1 (fr) 2002-10-17
JP2004534012A (ja) 2004-11-11
AR033458A1 (es) 2003-12-17
KR20040002898A (ko) 2004-01-07
GB0108775D0 (en) 2001-05-30
EP1373166A2 (fr) 2004-01-02
GB2374071A (en) 2002-10-09
WO2002081414A3 (fr) 2002-12-12

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